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Tracking the solid-state incorporation of Sn into the framework of dealuminated zeolite beta, and consequences for catalyst design

Tracking the solid-state incorporation of Sn into the framework of dealuminated zeolite beta, and consequences for catalyst design
Tracking the solid-state incorporation of Sn into the framework of dealuminated zeolite beta, and consequences for catalyst design

Sn-Beta has emerged as a state-of-the-art catalyst for a range of sustainable chemical transformations. Conventionally prepared by bottom-up hydrothermal synthesis methods, recent research has demonstrated the efficiency of several top-down methods of preparation. One attractive top-down approach is Solid-State Incorporation, where a dealuminated Beta zeolite is physically mixed with a solid Sn precursor, in particular Sn(ii) acetate, prior to heat treatment at 550 °C. This procedure is fast and benign, and metal incorporation requires no solvents and hence produces no aqueous Sn-containing waste streams. Although the performances of these catalysts have been well explored in recent years, the mechanism of heteroatom incorporation remains unknown, and hence, opportunities to improve the synthetic procedure via a molecular approach remain. Herein, we use a range of in situ spectroscopic techniques, alongside kinetic and computational methods, to elucidate the mechanisms that occur during preparation of the catalyst, and then improve the efficacy of the synthetic protocol. Specifically, we find that successful incorporation of Sn into the lattice occurs in several distinct steps, including (i) preliminary coordination of the metal ion to the vacant lattice sites of the zeolite during physical grinding; (ii) partial incorporation of the metal ion into the zeolite framework upon selective decomposition of the acetate ligands, which occurs upon heating the physical mixture in an inert gas flow from room temperature to 550 °C; and (iii) full isomorphous substitution of Sn into the lattice alongside its simultaneous oxidation to Lewis acidic Sn(iv), when the physically mixed material is exposed to air during a short (<1 h) isotherm period. Long isotherm steps are shown to be unnecessary, and fully oxidised Sn(iv) precursors are shown to be unsuitable for successful incorporation into the lattice. We also find that the formation of extra-framework Sn oxides is primarily dependent on the quantity of Sn present in the initial physical mixture. Based on these findings, we demonstrate a faster synthetic protocol for the preparation of Sn-Beta materials via Solid-State Incorporation, and benchmark their catalytic performance for the Meerwein-Ponndorf-Verley transfer hydrogenation reaction and the isomerisation of glucose to fructose.

2050-7488
22025-22041
Navar, Ricardo
3566c4e4-125b-41aa-8b02-e23741c02987
Tarantino, Giulia
118e6199-1899-414c-bdd8-47cf14cf31f0
Beynon, Owain T.
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Padovan, Daniele
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Botti, Luca
cf64f5d9-7104-4d02-a5a6-41c358f4f5dd
Gibson, Emma K.
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Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Owens, Alun
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Kondrat, Simon A.
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Logsdail, Andrew J.
2b65adf3-96a6-4e24-92cc-7025b89db7b6
Hammond, Ceri
fcbbcd87-a902-4259-8dff-9380c92aa603
Navar, Ricardo
3566c4e4-125b-41aa-8b02-e23741c02987
Tarantino, Giulia
118e6199-1899-414c-bdd8-47cf14cf31f0
Beynon, Owain T.
75114335-3410-43c3-bbc5-44ebee4183bc
Padovan, Daniele
1a2263ef-ea8f-4ac2-a613-886b2f130e58
Botti, Luca
cf64f5d9-7104-4d02-a5a6-41c358f4f5dd
Gibson, Emma K.
738c74e4-ab68-42fe-bda8-9d4a43669b31
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Owens, Alun
70e74048-2df6-4a2e-9e74-d414599b2757
Kondrat, Simon A.
8f09c877-8bb6-4c82-8f81-564085479aff
Logsdail, Andrew J.
2b65adf3-96a6-4e24-92cc-7025b89db7b6
Hammond, Ceri
fcbbcd87-a902-4259-8dff-9380c92aa603

Navar, Ricardo, Tarantino, Giulia, Beynon, Owain T., Padovan, Daniele, Botti, Luca, Gibson, Emma K., Wells, Peter P., Owens, Alun, Kondrat, Simon A., Logsdail, Andrew J. and Hammond, Ceri (2022) Tracking the solid-state incorporation of Sn into the framework of dealuminated zeolite beta, and consequences for catalyst design. Journal of Materials Chemistry A, 10 (41), 22025-22041. (doi:10.1039/d2ta03837d).

Record type: Article

Abstract

Sn-Beta has emerged as a state-of-the-art catalyst for a range of sustainable chemical transformations. Conventionally prepared by bottom-up hydrothermal synthesis methods, recent research has demonstrated the efficiency of several top-down methods of preparation. One attractive top-down approach is Solid-State Incorporation, where a dealuminated Beta zeolite is physically mixed with a solid Sn precursor, in particular Sn(ii) acetate, prior to heat treatment at 550 °C. This procedure is fast and benign, and metal incorporation requires no solvents and hence produces no aqueous Sn-containing waste streams. Although the performances of these catalysts have been well explored in recent years, the mechanism of heteroatom incorporation remains unknown, and hence, opportunities to improve the synthetic procedure via a molecular approach remain. Herein, we use a range of in situ spectroscopic techniques, alongside kinetic and computational methods, to elucidate the mechanisms that occur during preparation of the catalyst, and then improve the efficacy of the synthetic protocol. Specifically, we find that successful incorporation of Sn into the lattice occurs in several distinct steps, including (i) preliminary coordination of the metal ion to the vacant lattice sites of the zeolite during physical grinding; (ii) partial incorporation of the metal ion into the zeolite framework upon selective decomposition of the acetate ligands, which occurs upon heating the physical mixture in an inert gas flow from room temperature to 550 °C; and (iii) full isomorphous substitution of Sn into the lattice alongside its simultaneous oxidation to Lewis acidic Sn(iv), when the physically mixed material is exposed to air during a short (<1 h) isotherm period. Long isotherm steps are shown to be unnecessary, and fully oxidised Sn(iv) precursors are shown to be unsuitable for successful incorporation into the lattice. We also find that the formation of extra-framework Sn oxides is primarily dependent on the quantity of Sn present in the initial physical mixture. Based on these findings, we demonstrate a faster synthetic protocol for the preparation of Sn-Beta materials via Solid-State Incorporation, and benchmark their catalytic performance for the Meerwein-Ponndorf-Verley transfer hydrogenation reaction and the isomerisation of glucose to fructose.

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Accepted/In Press date: 30 August 2022
e-pub ahead of print date: 2 September 2022
Additional Information: Funding Information: CH gratefully appreciates financial support from The Royal Society through provision of a University Research Fellowship (UF140207, URF\R\201003) and enhanced research grant funding (RGF/EA/180314). CH also gratefully acknowledges support from The Engineering and Physical Sciences Research Council, for research funding (EP/T024712/1). RN gratefully appreciates financial support from CONACYT (Fellowship 472256). AJL gratefully appreciates funding by the UKRI Future Leaders Fellowship program (MR/T018372/1). The Diamond Light Source and RCaH are thanked for the provision of beamtime (SP12597-1), and Dr Diego Gianolio is thanked for experimental support. OTB gratefully appreciates financial support from the Coleg Cymraeg Cenedlaethol scholarship programme. Computing resources for this work were provided by ARCCA at Cardiff University, Supercomputing Wales, the Isambard 2 UK National Tier-2 HPC Service as funded by EPSRC (EP/T022078/1), and through membership of the UK's HPC Materials Chemistry Consortium (MCC), which is funded by EPRSC (EP/R029431). Publisher Copyright: © 2022 The Royal Society of Chemistry.

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Local EPrints ID: 474627
URI: http://eprints.soton.ac.uk/id/eprint/474627
ISSN: 2050-7488
PURE UUID: 0ff5e1c8-de69-4f47-a92e-5e6d8adc4f9d
ORCID for Peter P. Wells: ORCID iD orcid.org/0000-0002-0859-9172

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Date deposited: 28 Feb 2023 17:36
Last modified: 06 Jun 2024 01:43

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Contributors

Author: Ricardo Navar
Author: Giulia Tarantino
Author: Owain T. Beynon
Author: Daniele Padovan
Author: Luca Botti
Author: Emma K. Gibson
Author: Peter P. Wells ORCID iD
Author: Alun Owens
Author: Simon A. Kondrat
Author: Andrew J. Logsdail
Author: Ceri Hammond

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